CN102976650A - Set-retarding grinding aid for set-retarding cement and preparation method of set-retarding grinding aid - Google Patents
Set-retarding grinding aid for set-retarding cement and preparation method of set-retarding grinding aid Download PDFInfo
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- CN102976650A CN102976650A CN2012105125112A CN201210512511A CN102976650A CN 102976650 A CN102976650 A CN 102976650A CN 2012105125112 A CN2012105125112 A CN 2012105125112A CN 201210512511 A CN201210512511 A CN 201210512511A CN 102976650 A CN102976650 A CN 102976650A
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- grinding aid
- slow setting
- reaction
- cement
- setting grinding
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- 238000000227 grinding Methods 0.000 title claims abstract description 101
- 239000004568 cement Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 56
- 238000012986 modification Methods 0.000 claims abstract description 38
- 230000004048 modification Effects 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000005576 amination reaction Methods 0.000 claims abstract description 29
- 239000003999 initiator Substances 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 235000019357 lignosulphonate Nutrition 0.000 claims description 52
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 10
- 229920005610 lignin Polymers 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 6
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 6
- -1 Sunmorl N 60S Chemical compound 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000001509 sodium citrate Substances 0.000 claims description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 5
- 229940038773 trisodium citrate Drugs 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 9
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 239000003607 modifier Substances 0.000 abstract 4
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 230000003014 reinforcing effect Effects 0.000 abstract 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 abstract 1
- 238000000034 method Methods 0.000 description 27
- 230000015271 coagulation Effects 0.000 description 21
- 238000005345 coagulation Methods 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 238000010276 construction Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000006835 compression Effects 0.000 description 11
- 238000007906 compression Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000012467 final product Substances 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 7
- 229910052602 gypsum Inorganic materials 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 230000000979 retarding effect Effects 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 6
- 229920005551 calcium lignosulfonate Polymers 0.000 description 6
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 6
- 239000011083 cement mortar Substances 0.000 description 6
- 239000011396 hydraulic cement Substances 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- FOGYNLXERPKEGN-UHFFFAOYSA-N 3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfopropyl)phenoxy]propane-1-sulfonic acid Chemical class COC1=CC=CC(CC(CS(O)(=O)=O)OC=2C(=CC(CCCS(O)(=O)=O)=CC=2)OC)=C1O FOGYNLXERPKEGN-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 230000003467 diminishing effect Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 230000001934 delay Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 241000158728 Meliaceae Species 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 235000019691 monocalcium phosphate Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Abstract
The invention provides a set-retarding grinding aid for set-retarding cement and a preparation method of the set-retarding grinding aid. The set-retarding grinding aid provided by the invention comprises the following components in percent by weight: 20-30 percent of lignosulfonate, 5-8 percent of oxidant, 5-15 percent of graft modifier, 0.1-0.3 percent of initiator, 6-10 percent of amination modifier, 6-9 percent of formaldehyde, 4-8 percent of polar compound and the balance of water. According to the set-retarding grinding aid disclosed by the invention, the lignosulfonate is subjected to graft modification by using the graft modifier, and functional groups, such as carboxyl, hydroxyl and sulfonyl, which have a set-retarding reinforcing effect, are introduced; and in addition, amino is introduced in the lignosulfonate by the amination modifier, and therefore the surface activity of the lignosulfonate and the set-retarding effect of the grinding aid are improved.
Description
Technical field
The present invention relates to building material technical field, relate in particular to a kind of slow setting grinding aid for slow setting cement and preparation method thereof.
Background technology
Fast development along with the high-grade road traffic modernization construction, cement concrete pavement has been put into the critical positions of Road construction, and roadbed slow setting cement is used for highway subgrade, is used for Aggregate Stabilized with Cement, rubble, cement content is generally 5%, should not surpass 6% of compound total amount.Because the road construction spice, pave, the compacting equal time is longer, must finish before cement setting time arrives, the user is according to the requirement of site operation situation, and cement setting time needs to prolong, generally speaking should be greater than 3.5h according to the construction requirement jelling time, final setting time is not less than 6h.
Yet, because the characteristic of slow setting cement self and the inconvenience in the organization of production process thereof, this kind cement of direct production generally is reluctant in the cement mill, but obtain by following two kinds of approach: the one, when pulverizing cement, mix a small amount of retarded adhesive material, reach the purpose that delays cement setting time. but the serviceability of the retardant of being mixed reply concrete construction and weather resistance thereof, security have no adverse effects, disclose trolamine, sucrose, calcium superphosphate in the prior art, tripoly phosphate sodium STPP, Sunmorl N 60S, citric acid etc. use as retardant; The 2nd, when pulverizing cement, use the pretreated ardealite instead of process or Partial Replacement dihydrate gypsum as adjustable solidification agent, and mix again partially mixed material (such as Wingdale, flyash etc.), to reach the purpose that delays cement setting time.
But along with the fast development of motorway, because of the singularity of its construction, be not only to requirement is arranged its time of coagulation, the performances such as intensity of cement have also been proposed concrete requirement: require on the one hand initial set, final setting time longer; Require to use on the other hand the cement of large-sized rotary kiln factory production, the 3d of cement and 28d are more than needed, and ultimate compression strength must be stabilized between 4.0MPa ~ 7.0MPa.The slow setting cement that adopts above-mentioned dual mode to obtain can not improve the performances such as intensity of cement when guaranteeing the slow setting time, can't satisfy the needs of Modern High-Speed highway development, is unfavorable for its application.
Summary of the invention
The object of the present invention is to provide a kind of slow setting grinding aid for slow setting cement and preparation method thereof, slow setting grinding aid provided by the invention can delay the time of coagulation of cement, and improve the physicals of cement, be beneficial to its application in the construction such as high-grade highway.
The invention provides a kind of slow setting grinding aid for slow setting cement, comprise following component:
The sulfonated lignin of 20wt% ~ 30wt%;
The oxygenant of 3wt% ~ 10wt%;
The graft modification agent of 5wt% ~ 15wt%;
The initiator of 0.1wt% ~ 0.5wt%;
The amination modifying agent of 4wt% ~ 12wt%;
The formaldehyde of 3wt% ~ 12wt%;
The polar compound of 2wt% ~ 10wt%;
Surplus is water.
Preferably, described graft modification agent be vinylformic acid, methacrylic acid, maleic anhydride, vinylcarbinol, acrylamide and methylpropene sodium sulfonate one or more.
Preferably, described sulfonated lignin are sodium lignosulfonate or calcium lignin sulphonate.
Preferably, described oxygenant is one or more in hydrogen peroxide, potassium permanganate and the nitric acid.
Preferably, described initiator is one or more in ammonium persulphate, Sodium Persulfate and the Potassium Persulphate.
Preferably, described amination modifying agent be dimethylamine, quadrol and triethylenetetramine one or more.
Preferably, described polar compound be glycerol, Trisodium Citrate, Sunmorl N 60S, Diethylene Glycol and salicylic one or more.
The invention provides a kind of preparation method of the slow setting grinding aid for slow setting cement, may further comprise the steps:
A) described sulfonated lignin are mixed with oxygenant, carry out oxidizing reaction;
B) oxidation liquid that described step a) is obtained mixes with graft modification agent and initiator, carries out graft reaction;
C) under alkaline condition, graft reaction liquid and formaldehyde, amination modifying agent and polar compound reaction with described step b) obtains obtain the slow setting grinding aid.
Preferably, the temperature of oxidizing reaction is 80 ℃ ~ 100 ℃ in the described step a);
The time of described oxidizing reaction is 1h ~ 3h.
Preferably, described step c) is:
C1) the graft reaction liquid that described step b) is obtained mixes with alkaline matter, to wherein adding formaldehyde and amination modifying agent, obtains mixing solutions after the reaction;
C2) to described step c1) add polar compound in the mixing solutions that obtains, obtain the slow setting grinding aid after the reaction;
Described step c1) temperature of reaction in is 85 ℃ ~ 100 ℃, and the reaction times is 2h ~ 5h;
Described step c2) temperature of reaction in is 85 ℃ ~ 100 ℃, and the reaction times is 1h ~ 3h.
The invention provides a kind of slow setting grinding aid for slow setting cement and preparation method thereof, slow setting grinding aid provided by the invention comprises the sulfonated lignin of following component: 20wt% ~ 30wt%; The oxygenant of 3wt% ~ 10wt%; The graft modification agent of 5wt% ~ 15wt%; The initiator of 0.1wt% ~ 0.5wt%; The amination modifying agent of 4wt% ~ 12wt%; The formaldehyde of 3wt% ~ 12wt%; The polar compound of 2wt% ~ 10wt%; Surplus is water.In grinding aid provided by the invention, adopt the graft modification agent that sulfonated lignin are carried out graft modification, introduce the functional group that has in a large number the slow setting reinforced effects such as carboxyl, hydroxyl, sulfonic group etc.; And amido has been introduced in the amination modifying agent in sulfonated lignin, also can improve its grinding-aid effect, thereby improved the surfactivity of sulfonated lignin, improved the retarding effect that obtains grinding aid, prolonged the time of coagulation of cement, be beneficial to its application in the construction such as high-grade highway, and the cement that obtains has higher physicals, can improve the quality of high-grade highway, be beneficial to its application.Experimental result shows that slow setting grinding aid provided by the invention can delay cement setting time 3h ~ 5h, 3 days ultimate compression strength of cement has increased 2MPa ~ 4MPa, and ultimate compression strength had increased 4MPa ~ 7MPa in 28 days, had improved the performance of cement, and the effective usage quantity of diminishing grog, mix industrial residue more.
Embodiment
The invention provides a kind of slow setting grinding aid for slow setting cement, comprise following component:
The sulfonated lignin of 20wt% ~ 30wt%;
The oxygenant of 3wt% ~ 10wt%;
The graft modification agent of 5wt% ~ 15wt%;
The initiator of 0.1wt% ~ 0.5wt%;
The amination modifying agent of 4wt% ~ 12wt%;
The formaldehyde of 3wt% ~ 12wt%;
The polar compound of 2wt% ~ 10wt%;
Surplus is water.
Slow setting grinding aid provided by the invention adopts the graft modification agent that sulfonated lignin are carried out graft modification, introduces the functional group that has in a large number the slow setting reinforced effects such as carboxyl, hydroxyl, sulfonic group etc.; And amido has been introduced in the amination modifying agent in sulfonated lignin, also can improve its grinding-aid effect, thereby improved the surfactivity of sulfonated lignin, improved the retarding effect that obtains grinding aid, use it in the slow setting cement, prolong the time of coagulation of cement, and improved the physicals of cement, be beneficial to its application in the construction such as high-grade highway.
Slow setting grinding aid provided by the invention comprises the sulfonated lignin of 20wt% ~ 30wt%, is preferably 23wt% ~ 28wt%.Sulfonated lignin are anion surfactant, have good dispersiveness, heat-resistant stability and high temperature dispersibility, and grinding-aid effect is good, in this application, sulfonated lignin can reduce the surface energy of abrasive dust, overcome the magnetism between abrasive dust, reduce to pulverize resistance, stop and stick with paste ball paste mill, improve the flowability of abrasive dust, for cement brings preferably grinding-aid effect, improve mill efficiency, reduce energy consumption, slowed down condensing of cement, the application of slow setting grinding aid in slow setting cement that is conducive to obtain.The present invention to the source of described sulfonated lignin without limits, as adopting the commercial goods, in the present invention, described sulfonated lignin are preferably sodium lignosulfonate or calcium lignin sulphonate.In the prior art, sulfonated lignin mainly are prepared from by papermaking wastewater, the present invention is used for preparing the slow setting grinding aid with it, new approach is provided for the disposal and utilization of papermaking wastewater, have larger economy and the value of environmental protection, and the raw material sources of sulfonated lignin are extensive, cheap, reduced production cost.
Slow setting grinding aid provided by the invention comprises the oxygenant of 3wt% ~ 10wt%, is preferably 5wt% ~ 8wt%.In slow setting grinding aid provided by the invention, graft modification agent and amination modifying agent are carried out modification to sulfonated lignin, have improved the reactive behavior of sulfonated lignin behind the adding oxygenant.The present invention does not have special restriction to the kind of described oxygenant, adopts oxygenant well known to those skilled in the art to get final product.In the present invention, described oxygenant is preferably one or more in hydrogen peroxide, Peracetic Acid, potassium permanganate, ammonium persulphate, clorox and the nitric acid, more preferably one or more in hydrogen peroxide, potassium permanganate and the nitric acid;
Slow setting grinding aid provided by the invention comprises the graft modification agent of 5wt% ~ 15wt%, is preferably 8wt% ~ 12wt%.The present invention adopts the graft modification agent that sulfonated lignin are carried out modification, in the structure of sulfonated lignin, introduce the functional groups such as carboxyl, hydroxyl, sulfonic group, improve the surfactivity of sulfonated lignin, thereby improved the slow setting grinding-aid effect of sulfonated lignin.In the present invention, described graft modification agent is preferably one or more of vinylformic acid, methacrylic acid, maleic anhydride, vinylcarbinol, acrylamide, sodium allylsulfonate and methylpropene sodium sulfonate, more preferably one or more in vinylformic acid, vinylcarbinol, acrylamide, sodium allylsulfonate and the methylpropene sodium sulfonate;
Slow setting grinding aid provided by the invention comprises the initiator of 0.1wt% ~ 0.5wt%, is preferably 0.1wt% ~ 0.3wt%.In the present invention, the groups such as hydroxyl, carboxyl, sulfonic group are introduced in the reaction of described initiator initiation grafting properties-correcting agent and sulfonated lignin in the structure of sulfonated lignin, improve the surfactivity of sulfonated lignin, thereby improve its slow setting grinding-aid effect.The present invention does not have special restriction to the kind of described initiator, adopt initiator well known to those skilled in the art to get final product, in the present invention, described initiator is preferably persulphate, more preferably one or more in ammonium persulphate, Sodium Persulfate and the Potassium Persulphate;
Slow setting grinding aid provided by the invention comprises the amination modifying agent of 4wt% ~ 12wt%, more preferably 6wt% ~ 10wt%.Described amination modifying agent and sulfonated lignin react, and introduce amido in sulfonated lignin volume structure, further improve the grinding-aid effect of sulfonated lignin.In the present invention, described amination modifying agent is preferably one or more of dimethylamine, quadrol and triethylenetetramine, more preferably dimethylamine, quadrol or triethylenetetramine;
Slow setting grinding aid provided by the invention comprises the formaldehyde of 3wt% ~ 12wt%, is preferably 6wt% ~ 9wt%.In the present invention, described formaldehyde makes the surfactivity of the modified lignin mahogany sulfonate that obtains higher for the reaction condensing agent, has further improved the grinding-aid effect of slow setting grinding aid provided by the invention;
Slow setting grinding aid provided by the invention comprises the polar compound of 2wt% ~ 10wt%, more preferably 4wt% ~ 8wt%.In the present invention, polar compound can further improve the performance of the slow setting grinding aid that obtains as composite component.In the present invention, described polar compound be preferably multicomponent alcoholics compound, Trisodium Citrate, Sunmorl N 60S and salicylic one or more, more preferably glycerol, Trisodium Citrate, Sunmorl N 60S, Diethylene Glycol and salicylic one or more.
Slow setting grinding aid provided by the invention is except the described component of technique scheme, and surplus is water.The present invention does not have special restriction to described water, adopts water well known to those skilled in the art to get final product.
In slow setting grinding aid provided by the invention, adopt the graft modification agent that sulfonated lignin are carried out graft modification, introduce the functional group that has in a large number the slow setting reinforced effects such as carboxyl, hydroxyl, sulfonic group etc.; And amido has been introduced in the amination modifying agent in sulfonated lignin, thereby improved the surfactivity of sulfonated lignin, improved the retarding effect that obtains grinding aid, when using it in the slow setting cement, delay the time of coagulation of cement, be conducive to its application in the construction of high-grade highway etc.; And the slow setting grinding aid that provides of the present invention can improve the physicals of cement, is beneficial to its application.
The invention provides the preparation method of the described slow setting grinding aid of a kind of technique scheme, may further comprise the steps:
A) described sulfonated lignin are mixed with oxygenant, carry out oxidizing reaction;
B) oxidation liquid that described step a) is obtained mixes with graft modification agent and initiator, carries out graft reaction;
C) under alkaline condition, graft reaction liquid and formaldehyde, amination modifying agent and polar compound reaction with described step b) obtains obtain the slow setting grinding aid.
The present invention at first mixes sulfonated lignin with oxygenant, carry out oxidizing reaction, obtains oxidation liquid.The present invention preferably provides first the suspension of sulfonated lignin, then carries out oxidizing reaction to wherein adding oxygenant.The present invention does not have special restriction to the preparation method of described lignosulfonic acid salt suspensioning liquid, adopts the technical scheme of formulated suspension well known to those skilled in the art to get final product.The present invention preferably with sulfonated lignin with after water mixes, adopt supersound process, obtain the lignosulfonic acid salt suspensioning liquid.The mass percentage concentration of described lignosulfonic acid salt suspensioning liquid is preferably 40% ~ 60%, and more preferably 45% ~ 55%; The present invention does not have special restriction to described ultrasonic method, adopts ultrasonic technical scheme well known to those skilled in the art to get final product, and in the present invention, the described ultrasonic time is preferably 0.5h ~ 1.5h;
After obtaining the lignosulfonic acid salt suspensioning liquid, the present invention carries out oxidizing reaction to wherein adding oxygenant, has improved the reactive behavior of sulfonated lignin.The present invention is heated to 80 ℃ ~ 100 ℃ with the mixing solutions that obtains and carries out oxidizing reaction, more preferably 85 ℃ ~ 95 ℃ after preferably adding oxygenant in the described lignosulfonic acid salt suspensioning liquid; The time of described oxidizing reaction is preferably 1h ~ 3h, more preferably 1.5h ~ 2.5h.
After the present invention finishes above-mentioned oxidizing reaction, the present invention mixes the oxidation liquid that obtains with graft modification agent and initiator, carry out graft reaction, hydroxyl, carboxyl or sulfonic group in the structure of sulfonated lignin, have been introduced, improved the surfactivity of sulfonated lignin, thereby prolonged the time of coagulation of slow setting cement, but also improved its grinding-aid effect, thereby improved the physical strength of the slow setting cement that obtains.The present invention preferably prepares respectively first graft modification agent solution and initiator solution, then graft modification agent solution and initiator solution are dripped in the oxidation liquid that obtains such as above-mentioned technical scheme, described graft modification agent preferably dropwises in 1h ~ 3h, described initiator solution preferably dropwises in 3h ~ 5h, then the mixing solutions that obtains is carried out graft reaction under 80 ℃ ~ 100 ℃, more preferably 85 ℃ ~ 95 ℃; The time of described graft reaction is preferably 1h ~ 3h, more preferably 1.5h ~ 2.5h; The present invention does not have special restriction to the compound method of described graft modification agent solution and initiator solution, adopts the compounding process scheme of solution well known to those skilled in the art to get final product.
After finishing above-mentioned graft reaction, the present invention is under alkaline condition, and graft reaction liquid and formaldehyde, amination modifying agent and polar compound reaction with obtaining obtain the slow setting grinding aid for slow setting cement.The preferred graft reaction liquid that obtains to technique scheme first of the present invention mixes with alkaline matter, with described graft reaction liquid furnishing alkalescence, then to wherein adding formaldehyde and amination modifying agent, obtains mixing solutions after the reaction; In described mixing solutions, add polar compound, obtain the slow setting grinding aid after the reaction;
The present invention is in order to make the slow setting grinding aid that obtains have better retarding effect, preferred elder generation adds basic cpd in described graft reaction liquid, the pH value of described graft reaction liquid is transferred to 9 ~ 11, and then to wherein adding formaldehyde and amination modifying agent, obtain mixing solutions after the reaction.The present invention does not have special restriction to described alkaline matter, adopts alkaline matter well known to those skilled in the art to get final product.In the present invention, described alkaline matter is preferably basic cpd, oxyhydroxide more preferably, most preferably be sodium hydroxide or potassium hydroxide, the present invention can adopt alkaline matter, also can adopt the solution of alkaline matter, the massfraction of described alkaline substance solution is preferably 20% ~ 50%, and more preferably 25% ~ 40%; The temperature of described graft reaction liquid and formaldehyde and amination modifying agent reaction is preferably 85 ℃ ~ 100 ℃, more preferably 90 ℃ ~ 95 ℃; The time of reaction is preferably 2h ~ 5h, more preferably 3h ~ 4h;
After finishing the reaction of graft reaction liquid and formaldehyde and amination modifying agent, the present invention obtains the slow setting grinding aid with the mixing solutions and the polar compound reaction that obtain.The present invention preferably adds polar compound in described mixing solutions, after reacting, obtain the slow setting grinding aid.In the present invention, the temperature of described reaction is preferably 85 ℃ ~ 100 ℃, more preferably 95 ℃ ~ 95 ℃; The time of described reaction is preferably 1h ~ 3h, more preferably 1.5h ~ 2.5h.
After the present invention obtained the slow setting grinding aid, in order to test its performance, the present invention tested the slow setting grinding aid that obtains in Ф 500mm * little mill of 500m m standard test, and detailed process is as follows:
Grog according to following massfraction preparation material: 46wt%; The gypsum of 4.0wt% and the slag of 50wt%; Then be the slow setting grinding aid of 0.1wt% to adding material massfraction wherein; Carry out obtaining cement behind the grinding, according to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; Adopt the ventilative ratio surface area instrument of DBT-127 type Bo Shi to detect the Blain specific surface of the slow setting grinding aid that obtains; Detect consumptive use of water normal consistence, the time of coagulation of cement according to GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection ", the result shows, slow setting grinding aid provided by the invention, can delay cement setting time 3h ~ 5h, 3 days ultimate compression strength of cement has increased 2MPa ~ 4MPa, and ultimate compression strength had increased 4MPa ~ 7MPa in 28 days, had improved the performance of cement, and the effective usage quantity of diminishing grog, mix industrial residue more.
The invention provides a kind of slow setting grinding aid for slow setting cement, comprise the sulfonated lignin of following component: 20wt% ~ 30wt%; The oxygenant of 3wt% ~ 10wt%; The graft modification agent of 5wt% ~ 15wt%; The initiator of 0.1wt% ~ 0.5wt%; The amination modifying agent of 4wt% ~ 12wt%; The formaldehyde of 3wt% ~ 12wt%; The polar compound of 2wt% ~ 10wt%; Surplus is water.In grinding aid provided by the invention, adopt the graft modification agent that sulfonated lignin are carried out graft modification, introduce the functional group that has in a large number the slow setting reinforced effects such as carboxyl, hydroxyl, sulfonic group etc.; And amido has been introduced in the amination modifying agent in sulfonated lignin, thereby improved the surfactivity of sulfonated lignin, improved the retarding effect that obtains grinding aid, when using it in the slow setting cement, can prolong the time of coagulation of cement, thereby be conducive to its application in the construction such as high-grade highway.And slow setting grinding aid provided by the invention can improve the physicals of cement effectively when delaying cement setting time, keeping can reducing the consumption of cement clinker in the constant situation of original strength of cement, mixes blended material more.Experimental result shows that slow setting grinding aid provided by the invention can delay cement setting time 3h ~ 5h, 3 days ultimate compression strength of cement has increased 2MPa ~ 4MPa, and ultimate compression strength had increased 4MPa ~ 7MPa in 28 days, had improved the performance of cement, and the effective usage quantity of diminishing grog, mix industrial residue more.
In addition, slow setting grinding aid provided by the invention adds convenient, and easy handling brings great convenience for the production of slow setting cement; And the slow setting grinding aid that obtains has higher water-soluble, free from extraneous odour, nontoxic, is green product; The main raw material that adopts is sulfonated lignin, and cost is low, and low price, its main source are papermaking wastewater, for the utilization of papermaking wastewater provides a new approach, is conducive to environmental protection.
And slow setting grinding aid provided by the invention is for the enterprise that has used cement grinding aid, need not to increase to set, and only needs to change a grinding aid kind and can produce slow setting cement.
In order to further specify the present invention, below in conjunction with embodiment slow setting grinding aid for slow setting cement provided by the invention and preparation method thereof is described in detail, but they can not be interpreted as restriction to protection domain of the present invention.
Embodiment 1
The calcium lignin sulphonate of 82g is dissolved in the 80g water, and constantly stirs, until completely dissolved, put into ultrasonic instrument and process 1h with ultrasonic wave, obtain calcium lignosulfonate solution;
Described calcium lignosulfonate solution is heated to 85 ℃, then to wherein adding 18g potassium permanganate and 6g concentrated nitric acid reaction 2h, obtains reaction soln;
Again 12g sodium allylsulfonate, 14g propionic acid amide, 10g vinylformic acid and the preparation of 60g water are obtained graft modification agent solution (being called for short A solution), the Sodium Persulfate of 0.7g and the water of 20g are made into initiator solution (being called for short B) solution;
Above-mentioned reaction soln is warmed up to 95 ℃, and to wherein dripping A solution and B solution, A solution drips off in 3h, and B solution is added dropwise to complete in 4h, then with the mixing solutions insulation 1h that obtains;
Being 30% sodium hydroxide solution with massfraction transfers to the pH value of mixing solutions about 9, to wherein adding 34g triethylenetetramine and 37g formaldehyde, and at 95 ℃ of lower back flow reaction 2h, again to wherein adding 20g Sunmorl N 60S and 12g glycerol and being incubated 1h, namely obtain the slow setting grinding aid thereafter.
The present invention tests the slow setting grinding aid that obtains in Ф 500mm * little mill of 500mm standard test, detailed process is as follows:
Mix according to following material proportion: massfraction is that 46% grog, massfraction are 4.0% gypsum, the slag of massfraction 50%, add massfraction in the mixture that obtains and be the slow setting grinding aid that the present embodiment of mixture total mass 0.1% obtains, the cement after obtaining behind the combined grinding processing.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; Adopt the ventilative ratio surface area instrument of DBT-127 type Bo Shi to detect the Blain specific surface of the slow setting grinding aid that obtains; According to consumptive use of water normal consistence, the time of coagulation of GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " detection cement, the result is as shown in table 1, and table 1 is the little mill experimental result that the embodiment of the invention and comparative example obtain.
Embodiment 2
The calcium lignin sulphonate of 90g is dissolved in the 80g water, and constantly stirs, until completely dissolved, put into ultrasonic instrument and process 1h with ultrasonic wave, obtain calcium lignosulfonate solution;
Described calcium lignosulfonate solution is heated to 80 ℃, then to wherein adding 28g hydrogen peroxide reaction 2h, obtains reaction soln;
With the 20g maleic anhydride, 18g methylpropene sodium sulfonate, 6g vinylformic acid and 64g water are made into certain graft modification agent solution (being called for short A solution) again, and the ammonium persulphate of 0.8g and the water of 20g are made into initiator solution (being called for short B) solution;
Above-mentioned reaction soln is warmed up to 95 ℃, and to wherein dripping A solution and B solution, A solution drips off in 2h, and B solution is added dropwise to complete in 3h, then with the mixing solutions insulation 1h that obtains;
Being 30% sodium hydroxide solution with massfraction transfers to the pH value of described mixing solutions about 9, to wherein adding 29g quadrol and 32g formaldehyde and at 95 ℃ of lower back flow reaction 2h, again to wherein add 18g Trisodium Citrate and 10g Whitfield's ointment and be incubated 1h, namely obtain slow setting grinding aid thereafter.
The present invention tests the slow setting grinding aid that obtains in Ф 500mm * little mill of 500mm standard test, detailed process is as follows:
Mix according to following material proportion: massfraction is that 46% grog, massfraction are 4.0% gypsum, the slag of massfraction 50%, add massfraction in the mixture that obtains and be the slow setting grinding aid that the present embodiment of mixture total mass 0.1% obtains, the cement after obtaining behind the combined grinding processing.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; Adopt the ventilative ratio surface area instrument of DBT-127 type Bo Shi to detect the Blain specific surface of the slow setting grinding aid that obtains; According to consumptive use of water normal consistence, the time of coagulation of GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " detection cement, the result is as shown in table 1, and table 1 is the little mill experimental result that the embodiment of the invention and comparative example obtain.
Embodiment 3
The calcium lignin sulphonate of 77g is dissolved in the 80g water, and constantly stirs, until completely dissolved, put into ultrasonic instrument and process 1h with ultrasonic wave, obtain calcium lignosulfonate solution;
Described calcium lignosulfonate solution is heated to 80 ℃, is 30% hydrogen peroxide reaction 2h to wherein adding the 20g massfraction then, obtains reaction soln;
With the 21g methylpropene sodium sulfonate, 15g vinylcarbinol, 15g acrylamide and 64g water are made into certain graft modification agent solution (being called for short A solution) again, and the ammonium persulphate of 1.0g and the water of 20g are made into initiator solution (being called for short B) solution;
Being 30% sodium hydroxide solution with massfraction transfers to the pH value of described reaction soln about 9, it is warmed up to 95 ℃, and to wherein dripping A solution and B solution, A solution drips off in 2h, B solution is added dropwise to complete in 3h, then with the mixing solutions insulation 1h that obtains;
After insulation is finished, add again 31g dimethylamine and 37g formaldehyde in the mixing solutions and at 95 ℃ of lower back flow reaction 2h, again to wherein adding 8g glycerol, 7g Diethylene Glycol and 17g Whitfield's ointment and being incubated 1h, namely obtain the slow setting grinding aid thereafter.
The present invention tests the slow setting grinding aid that obtains in Ф 500mm * little mill of 500mm standard test, detailed process is as follows:
Mix according to following material proportion: massfraction is that 46% grog, massfraction are 4.0% gypsum, the slag of massfraction 50%, add massfraction in the mixture that obtains and be the slow setting grinding aid that the present embodiment of mixture total mass 0.1% obtains, the cement after obtaining behind the combined grinding processing.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; Adopt the ventilative ratio surface area instrument of DBT-127 type Bo Shi to detect the Blain specific surface of the slow setting grinding aid that obtains; According to consumptive use of water normal consistence, the time of coagulation of GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " detection cement, the result is as shown in table 1, and table 1 is the little mill experimental result that the embodiment of the invention and comparative example obtain.
Comparative example 1
Cement after obtaining processing behind the slag combined grinding with the gypsum of the grog of 46wt%, 4.0wt% and 50wt%.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; Adopt the ventilative ratio surface area instrument of DBT-127 type Bo Shi to detect the Blain specific surface of the slow setting grinding aid that obtains; According to consumptive use of water normal consistence, the time of coagulation of GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " detection cement, the result is as shown in table 1, and table 1 is the little mill experimental result that the embodiment of the invention and comparative example obtain.
Comparative example 2
The gypsum of the grog of 46wt%, 4.0wt% and the slag of 50wt% are mixed, then to 0.1% the calcium lignin sulphonate that wherein adds the mixture total mass, the cement after obtaining behind the grinding processing.According to GB/T 17671-1999 " Test method for strength of hydraulic cement mortar (ISO method) " test strength of cement mortar; Adopt the ventilative ratio surface area instrument of DBT-127 type Bo Shi to detect the Blain specific surface of the slow setting grinding aid that obtains; According to consumptive use of water normal consistence, the time of coagulation of GB 1346-2001 " cement normal consistency water consumption, time of coagulation, the stability method of inspection " detection cement, the result is as shown in table 1, and table 1 is the little mill experimental result that the embodiment of the invention and comparative example obtain.
The little mill experimental result that table 1 embodiment of the invention and comparative example obtain
As can be seen from Table 1, slow setting grinding aid provided by the invention can increase the specific surface area of cement, delays cement setting time 3h ~ 5h, and 3 days ultimate compression strength of cement has increased 2MPa ~ 4MPa, and ultimate compression strength had increased 4MPa ~ 7MPa in 28 days.This explanation, slow setting grinding aid provided by the invention can prolong the time of coagulation of cement, when using it in the slow setting cement, is conducive to its application in the construction such as high-grade highway; And slow setting grinding aid provided by the invention can effectively improve the physicals of cement when delaying cement setting time, keeping can reducing cement clinker consumption in the constant situation of original strength of cement, mixes blended material more, is beneficial to its application.
As seen from the above embodiment, the invention provides a kind of slow setting grinding aid for slow setting cement and preparation method thereof, slow setting grinding aid provided by the invention comprises the sulfonated lignin of following component: 20wt% ~ 30wt%; The oxygenant of 3wt% ~ 10wt%; The graft modification agent of 5wt% ~ 15wt%; The initiator of 0.1wt% ~ 0.5wt%; The amination modifying agent of 4wt% ~ 12wt%; The formaldehyde of 3wt% ~ 12wt%; The polar compound of 2wt% ~ 10wt%; Surplus is water.In grinding aid provided by the invention, adopt the graft modification agent that sulfonated lignin are carried out graft modification, introduce the functional group that has in a large number the slow setting reinforced effects such as carboxyl, hydroxyl, sulfonic group etc.; And amido has been introduced in the amination modifying agent in sulfonated lignin, also can improve its retarding effect, thereby improved the surfactivity of sulfonated lignin, improved the retarding effect that obtains grinding aid, prolonged the time of coagulation of cement, use it in the slow setting cement, be conducive to its application in the construction such as high-grade highway; And slow setting grinding aid provided by the invention can also improve the physicals of cement when slowing down cement setting, be beneficial to its application.Experimental result shows that slow setting grinding aid provided by the invention can delay cement setting time 3h ~ 5h, 3 days ultimate compression strength of cement has increased 2MPa ~ 4MPa, and ultimate compression strength had increased 4MPa ~ 7MPa in 28 days, had improved the performance of cement, and the effective usage quantity of diminishing grog, mix industrial residue more.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. slow setting grinding aid that is used for slow setting cement comprises following component:
The sulfonated lignin of 20wt% ~ 30wt%;
The oxygenant of 3wt% ~ 10wt%;
The graft modification agent of 5wt% ~ 15wt%;
The initiator of 0.1wt% ~ 0.5wt%;
The amination modifying agent of 4wt% ~ 12wt%;
The formaldehyde of 3wt% ~ 12wt%;
The polar compound of 2wt% ~ 10wt%;
Surplus is water.
2. slow setting grinding aid according to claim 1 is characterized in that, described graft modification agent is one or more of vinylformic acid, methacrylic acid, maleic anhydride, vinylcarbinol, acrylamide and methylpropene sodium sulfonate.
3. slow setting grinding aid according to claim 1 is characterized in that, described sulfonated lignin are sodium lignosulfonate or calcium lignin sulphonate.
4. slow setting grinding aid according to claim 1 is characterized in that, described oxygenant is one or more in hydrogen peroxide, potassium permanganate and the nitric acid.
5. slow setting grinding aid according to claim 1 is characterized in that, described initiator is one or more in ammonium persulphate, Sodium Persulfate and the Potassium Persulphate.
6. slow setting grinding aid according to claim 1 is characterized in that, described amination modifying agent is one or more of dimethylamine, quadrol and triethylenetetramine.
7. slow setting grinding aid according to claim 1 is characterized in that, described polar compound be glycerol, Trisodium Citrate, Sunmorl N 60S, Diethylene Glycol and salicylic one or more.
8. preparation method who is used for the slow setting grinding aid of slow setting cement may further comprise the steps:
A) described sulfonated lignin are mixed with oxygenant, carry out oxidizing reaction;
B) oxidation liquid that described step a) is obtained mixes with graft modification agent and initiator, carries out graft reaction;
C) under alkaline condition, graft reaction liquid and formaldehyde, amination modifying agent and polar compound reaction with described step b) obtains obtain the slow setting grinding aid.
9. preparation method according to claim 8 is characterized in that, the temperature of oxidizing reaction is 80 ℃ ~ 100 ℃ in the described step a);
The time of described oxidizing reaction is 1h ~ 3h.
10. preparation method according to claim 8 is characterized in that, described step c) is:
C1) the graft reaction liquid that described step b) is obtained mixes with alkaline matter, to wherein adding formaldehyde and amination modifying agent, obtains mixing solutions after the reaction;
C2) to described step c1) add polar compound in the mixing solutions that obtains, obtain the slow setting grinding aid after the reaction;
Described step c1) temperature of reaction in is 85 ℃ ~ 100 ℃, and the reaction times is 2h ~ 5h;
Described step c2) temperature of reaction in is 85 ℃ ~ 100 ℃, and the reaction times is 1h ~ 3h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2980038A4 (en) * | 2013-03-26 | 2016-12-14 | Kao Corp | Method for improving strength of hydraulic composition hardened product |
| CN106316186A (en) * | 2016-08-24 | 2017-01-11 | 盐城工学院 | Inorganic super setting retarder and preparing method and application thereof |
| CN108164174A (en) * | 2017-12-04 | 2018-06-15 | 杨忠华 | A kind of preparation method of cement grinding aid |
| CN108940553A (en) * | 2018-07-19 | 2018-12-07 | 佛山陵朝新材料有限公司 | A kind of ore crushing grinding aid special |
| CN115746330A (en) * | 2022-11-08 | 2023-03-07 | 安徽成弘建新材料有限公司 | Modified alkali lignin, preparation method thereof, semi-coke grinding aid and use method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805147A (en) * | 2010-03-29 | 2010-08-18 | 山东宏艺科技股份有限公司 | Preparation method of liquid cement grinding aid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101805147A (en) * | 2010-03-29 | 2010-08-18 | 山东宏艺科技股份有限公司 | Preparation method of liquid cement grinding aid |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2980038A4 (en) * | 2013-03-26 | 2016-12-14 | Kao Corp | Method for improving strength of hydraulic composition hardened product |
| CN106316186A (en) * | 2016-08-24 | 2017-01-11 | 盐城工学院 | Inorganic super setting retarder and preparing method and application thereof |
| CN108164174A (en) * | 2017-12-04 | 2018-06-15 | 杨忠华 | A kind of preparation method of cement grinding aid |
| CN108940553A (en) * | 2018-07-19 | 2018-12-07 | 佛山陵朝新材料有限公司 | A kind of ore crushing grinding aid special |
| CN115746330A (en) * | 2022-11-08 | 2023-03-07 | 安徽成弘建新材料有限公司 | Modified alkali lignin, preparation method thereof, semi-coke grinding aid and use method thereof |
| CN115746330B (en) * | 2022-11-08 | 2024-02-20 | 安徽成弘建新材料有限公司 | Modified alkali lignin, preparation method thereof, semi-coke grinding aid and use method thereof |
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Inventor after: Zhao Hongyi Inventor after: Li Chengwu Inventor after: Meng Fanjun Inventor after: Zhong Xuanshu Inventor after: Zhu Huayu Inventor after: Zhu Kongzan Inventor after: Yin Junfeng Inventor after: Song Nanjing Inventor after: Feng Enjuan Inventor after: Fu Xiuxin Inventor before: Zhao Hongyi Inventor before: Meng Fanjun Inventor before: Zhu Huayu Inventor before: Zhu Kongzan Inventor before: Yin Junfeng Inventor before: Song Nanjing Inventor before: Feng Enjuan Inventor before: Fu Xiuxin Inventor before: Li Chengwu |
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Free format text: CORRECT: INVENTOR; FROM: ZHAO HONGYI MENG FANJUN ZHU HUAYU ZHU KONGZAN YIN JUNFENG SONG NANJING FENG ENJUAN FU XIUXIN LI CHENGWU TO: ZHAO HONGYI MENG FANJUN ZHONG XUANSHU ZHU HUAYU ZHU KONGZAN YIN JUNFENG SONG NANJING FENG ENJUAN FU XIUXIN LI CHENGWU |
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Effective date of registration: 20150929 Address after: 276034 No. 369 Renmin Street, Hedong District, Shandong, Linyi Patentee after: Shandong Hongyi Technology Co., Ltd. Address before: 276034 No. 369 Renmin Street, Hedong District, Shandong, Linyi Patentee before: Shandong Hongyi Technology Co., Ltd. Patentee before: Linyi University |
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Address after: 276034 north of the intersection of Wenquan road and Fenghuang street, Fenghuangling sub district office, Hedong, Linyi City, Shandong Province Patentee after: LINYI HONGYI TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: 276034 No. 369 Renmin Street, Hedong District, Shandong, Linyi Patentee before: SHANDONG HONGYI TECHNOLOGY Co.,Ltd. |
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Address after: 276000 north of the intersection of Wenquan road and Fenghuang street, Fenghuangling sub district office, Hedong, Linyi City, Shandong Province Patentee after: Linyi conch New Material Technology Co.,Ltd. Address before: 276034 north of the intersection of Wenquan road and Fenghuang street, Fenghuangling sub district office, Hedong, Linyi City, Shandong Province Patentee before: LINYI HONGYI TECHNOLOGY DEVELOPMENT Co.,Ltd. |
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